CN1189522C - Composition for used as reinforcing filler in polymer composition - Google Patents
Composition for used as reinforcing filler in polymer composition Download PDFInfo
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- CN1189522C CN1189522C CN00812361.6A CN00812361A CN1189522C CN 1189522 C CN1189522 C CN 1189522C CN 00812361 A CN00812361 A CN 00812361A CN 1189522 C CN1189522 C CN 1189522C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
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Abstract
The invention concerns a composition for use as reinforcing filler in polymer compositions, obtained by drying, in particular by atomisation, of a suspension derived from a mixture of mineral or organic particles having a form factor less than 15 and a suspension of organic and mineral particles dispersible in a polymer medium. The invention also concerns polymer compositions comprising said filler and finished articles based on such compositions.
Description
The present invention relates to can be as the composition of the reinforcing filler in the polymer composition, and said composition obtains by dry suspension, this suspension comprise form factor less than 15 particle and can be in polymeric media divided particles.
The present invention also relates to comprise the polymer composition of said composition.
At last, the present invention relates to the finished product based on these polymer compositions in addition.
Known in polymkeric substance, particularly in elastomerics, adopt white reinforcing filler, particularly precipitated silica.
Generally speaking, be known as acquisition and strengthen the property, in polymeric matrix, must cut apart filler as far as possible carefully and divide cloth filler as far as possible equably by the best that filler provides.Yet, only under following situation, can reach such condition: on the one hand, with polymer blending during filler be very easy to be incorporated into (the mixing property of filler) in the matrix, and very easy deagglomeration is very thin form of powder (deagglomeration of filler), on the other hand, the powder that is obtained by aforementioned deagglomeration process, then, self is fabulous and be evenly dispersed in (dispersion of powder) in the polymkeric substance.
In addition, because mutual avidity, in elastomer matrix, filler grain may distressful trend be that their can be coalescent each other.If in fact obtain all polymkeric substance/filler interaction that can produce in blend operating period, the unwanted results that these fillers/the filler interaction has is to be restricted to strengthening the property to be lower than the level that can reach in theory substantially.
In addition, in virgin state, such interaction tends to increase the rigidity and the denseness of mixture, therefore makes them more be difficult to processing.
For some time, special use can be in polymeric media the dispersive precipitated silica, promptly it has high dispersibility in its applicating medium.
Also can use the binding substances of filler, it is to be every kind of filler of solid form by direct blend, and for example aluminum oxide and dispersible precipitated silica obtain.Yet, when using this binding substances, the limited dispersibility of one of filler occurs suddenly once more in applicating medium, and strengthening the property of the polymer composition that obtains is always not gratifying: observe diameter and may reach about 10 microns agglomeration material at the most in these polymer compositions, therefore having mixed additive in these polymer compositions, is deleterious agglomerates for these composition properties.
The purpose of this invention is to provide a kind of composition, said composition is prepared by at least two kinds of components in special mode, wherein a kind of component can be disperseed in polymeric media, another component preferably can not be disperseed in such medium, with said composition as the filler in the polymer composition, in the latter, reach in mechanical property, gratifying trading off between rheological property and the dynamic property, and obtain as filler with the direct blends of using every kind of component with solid form those compare, said composition especially makes these polymer compositions have improved performance.
For reaching this purpose, the invention provides a kind of composition that obtains by dry suspension (being generally aqeous suspension), this suspension comprises, on the one hand, form factor less than 15 inorganic or organic filler A and, on the other hand, can be in polymeric media the inorganic or organic filler B of dispersive.
Generally speaking, composition according to the present invention prepares by dry suspension, this suspension is by mixing suspension (be generally aqeous suspension) and at least a can in polymeric media the suspension (be generally aqeous suspension) of dispersive organic or inorganic particle B obtain of at least a form factor less than 15 inorganic or organic filler A; That is to say, the general suspension that passes through dry altogether two kinds of particle A and B, and make according to composition of the present invention.
Can use each in these two kinds of suspension by the form of suspension that directly obtains from the method that is used to prepare particle A or B.
Also can pass through the particle A or the B of redispersion solid form (dried forms) in liquid medium, and obtain in these two kinds of suspension each.Particle A and/or B can carry out surface treatment in advance, at least in part.
For the mixing of two kinds of suspension, may preferably include homogenization operation or allow the processing of particle deagglomeration, for example wet mixing refining, or ultrasonication for example; Generally speaking, this homogenization operation is made up of mechanical stirring.
During mixing, also can add stablizer, for example hydrocolloid.
Can use self known any measure to carry out drying (or dry altogether) operation.
Yet the highly useful embodiment according to the present invention is carried out drying by spraying (spraying altogether), promptly by in hot atmosphere with suspension spray (spraying drying).Therefore, composition according to the present invention can be described as " spray material altogether ".The spraying gun temperature out that adopts is usually less than 170 ℃, preferably less than 140 ℃ with for example be 100-135 ℃.Can be by the suitable atomisers of any kind, the turbine spraying gun that particularly has nozzle carries out drying; Preferably adopt the nozzle atomization device, particularly adopt those of liquid pressure.
According to the present invention, the composition that obtains after drying operation is solid (drying) form.Particularly when carrying out drying by the nozzle atomization device, composition can be the form of almost spherical pearl, and its mean sizes can be at least 80 μ m, particularly is at least 100 μ m, for example is at least 150 μ m; This size generally is at most 300 μ m.According to NF * 11507 (in December, 1970) standard,, and measure this mean sizes by the drying screening with by the diameter of measurement corresponding to 50% cumulative oversize.
After drying operation, as needs, the composition that obtains can be carried out mixing step or other forming step, for example granulation, compress or extrusion step.
Being used for preparing the inorganic of thing combined according to the invention or organic filler A and B at first is dispersible at suspension medium, and possible is, as needs, by using additive or after treatment aids in dispersion.
Inorganic or organic filler A has form factor, and the average largest dimensions that this form factor is defined as particle A less than 15, particularly is at most 12 to the ratio of the minimum average B configuration size of particle A.
Generally speaking, the average aggregate size of particle A is less than 1 μ m, particularly less than 0.8 μ m, for example less than 0.5 μ m.
The particle A that is used to prepare thing combined according to the invention at first is preferably inorganic particulate.
Therefore, these particles A can be pure aluminium silicate or TiO 2 particles.
These particles A also can be hydroxyl aluminium carbonate or magnesium, hydroxyl oxygen aluminium carbonate or magnesium or oxo aluminium carbonate or magnesium particle or hydrotalcite particle.
Preferably, particle A is an aluminium oxide particles.
According to variation of the present invention, especially under the situation that at least a acid exists, acetate (for example, acetate/Al particularly
2O
3Mol ratio is 1.5-5, particularly 2-4), can obtain this aluminum oxide by the suspension of hot-pressing processing boehmite or preferred pseudobochmite.Generally speaking, hot-pressing processing is carried out under 110-150 ℃ maintenance temperature, and this keeps temperature to continue 6-10 hour.Optionally, after this hot-pressing processing, can carry out chemistry and/or hot aftertreatment (for example, neutralization or calcining).
According to another kind of variation the of the present invention, this aluminum oxide is the crystallization monohydrate, mainly is the form of boehmite, and it is by obtaining sodium aluminate and Tai-Ace S 150 co-precipitation.
The particle A that is used for preparing thing combined according to the invention at first generally can not disperse at applicating medium, promptly can not disperse in polymeric media, and these are different with particle B.Yet, it has surprisingly been found that because the preparation method of thing combined according to the invention wherein when this composition during as the filler in the polymer composition, the dispersibility of particle A generally is improved substantially; Therefore have been found that, in the photo that obtains by scanning electronic microscope, in this way in the polymer composition of blast blending, do not detect agglomerate or aggregate, or only detect considerably less agglomerate or aggregate, yet comprise at polymer composition under the situation of direct blends of the particle A of solid form and particle B, observe the agglomeration material of significant quantity, may reach about 10 microns diameter as filler; Therefore can significantly improve the macro-dispersion quality of particle B (being under the situation of aluminum oxide at it especially) in rubber combination.
The particle B that is used for preparing thing combined according to the invention at first can disperse at polymeric media, and promptly in their applicating medium, they have high dispersibility.
In the present invention, the chemical property of particle A and particle B different (for example, if particle A is a TiO 2 particles, then particle B forms (being equal to or not being equal to the particle A that this forms) by titanium dioxide).
Preferably, particle B is by at polymeric media, particularly be made up of the precipitated silica particle of high dispersibility in elastomerics.
As mentioned above, in elastomerics, have these precipitated silica particles of high dispersibility, can be directly from the form of the suspension of its preparation method, and be used for preparation according to composition of the present invention.After preparing they of solid form, also can be by in medium, their redispersion being used.
In suitable precipitated silica, what can mention is at application EP 0 520 862, that describe among WO 95/09127 and the WO 95/09128 or that obtain by method shown in these applications those.
For example, can the selective precipitation silicon dioxide granule, for example form is those of almost spherical pearl, particularly mean sizes is at least 80 μ m, the pore distribution that has makes that by diameter be the pore volume that the hole of 175-275 dust forms, and is at least by diameter to be less than or equal to 50% of pore volume that the hole of 400 dusts forms.
Also can select such precipitated silica particle, it has the ultrasonic wave deagglomeration factor (F greater than 5.5ml
D) and after the ultrasonic wave deagglomeration less than the middle footpath ( of 5 μ m
50); Preferably, the pore distribution that described then precipitated silica particle has in addition makes that by diameter be the pore volume that the hole of 175-275 dust forms, and is at least by diameter to be less than or equal to 50% of pore volume that the hole of 400 dusts forms.
Also can select such precipitated silica particle, it has the ultrasonic wave deagglomeration factor (F greater than 11ml
D) and after the ultrasonic wave deagglomeration less than the middle footpath ( of 2.5 μ m
50).
By mercury porosimetry metering orifice volume; Being prepared as follows of each sample: in baking oven, under 200 ℃,, from baking oven, taking out within 5 minutes, sample is placed in the test cabinet then predrying 2 hours of each sample, and vacuum outgas, for example use rotating vane pump; Adopt 140 ° contact angle θ and the surface tension γ of 484 dyne/cm (MICROMERICS 9300 porosimeters), calculate bore dia from the Washburn formula.
Dispersibility by the test evaluation precipitated silica that carries out according to following scheme:
Measure (by the laser differential) by the size of particles that on the silica suspension that carries out the ultrasonic wave deagglomeration in advance, carries out, the interior poly-situation of assessment agglomerate; Therefore in this way, measure the deagglomeration situation (be crushed to be of a size of tens microns with material 0.1) of silicon-dioxide.Be equipped with VIBRACELL BIOBLOCK (600W) the ultrasonic degradation device (sonificator) that the 19mm diameter is popped one's head in by use, carry out the ultrasonic wave deagglomeration.Use SYMPATEC particle size analysis instrument, carry out size of particles by the laser differential and measure.
At the pill box (highly: 6cm and diameter: 4cm) 2g silicon-dioxide weighed and weight is become 50g by adding deionized water; Therefore produce 4% aqueous silica suspension, by magnetic agitation with its homogenizing 2 minutes., as follows carry out ultrasonic wave deagglomeration operation thereafter: the length that makes probe immerse 4cm, regulate output rating and make the needle deflection of power scale card arrive the point of expression 20%.Deagglomeration was carried out 420 seconds.The homogenizing suspension of known volume (with ml represent) put into the container of particle size analysis instrument after, carry out size of particles measure thereafter.
The middle footpath that obtains
50Numerical value is low more, and the dispersibility of silicon-dioxide/deagglomeration ability is high more.Also meter proportion (10 * introduce suspension vol (in ml))/(optical density (OD) of the suspension that is detected by the particle size analysis instrument), this optical density (OD) is about 20.This ratio is the indication of size less than 0.1 μ m particle content, and it be can't help the particle size analysis instrument and detects.This ratio (is called the ultrasonic wave deagglomeration factor (F
D)) high more, the dispersibility/deagglomeration of silicon-dioxide is high more.
The CTAB specific surface area that can be used for precipitated silica particle of the present invention is 50-240m
2/ g, be preferably 100-240m
2/ g and be in particular 140-240m
2/ g; Therefore it can be 140-200m
2/ g, for example 140-170m
2/ g.The CTAB specific surface area is the external surface area according to NF T45007 (in November, 1987) (5.12) canonical measure.
For preparation according to composition of the present invention, the amount of the particle B that uses as 0.1-99.9wt% and, particularly when particle B is the precipitated silica particle, be preferably 50-98wt%, 60-85wt% for example is based on the particle A of use and the total amount of B.
A useful especially purposes of thing combined according to the invention is as the reinforcing filler in the polymer composition.In polymer composition, it reaches gratifying the trading off between mechanical property, rheological property and dynamic property, those that obtain as filler with the direct blends of particle A that uses solid form and particle B are compared, and these performances are improved.
Described polymer composition particularly based on one or more elastomericss (especially thermoplastic elastomer), preferably has-150 ℃ to+300 ℃ second-order transition temperature generally based on one or more polymkeric substance or multipolymer, for example-150 ℃ to 20 ℃.In this polymer composition, be used as reinforcing filler according to composition of the present invention, and this polymer composition constitutes another theme of the present invention.
As possible polymkeric substance, what can mention especially is diene polymer, particularly diene elastomer.
For example, what can mention is natural rubber, derived from polymkeric substance or multipolymer, butyl polyacrylate or its binding substances of aliphatics that comprises at least one unsaturated group or aromatic monomer (particularly for example, ethene, propylene, divinyl, isoprene and vinylbenzene); What also can mention is silicone elastomer and halogenated polymer.
Polymkeric substance (multipolymer) can be mass polymer (multipolymer), polymkeric substance (multipolymer) latex or polymkeric substance (multipolymer) solution in water or in any other suitable dispersion liquid.
Described polymer composition can be by sulphur-sulfurized.
Generally speaking, they comprise at least a coupling agent and/or at least a restorative in addition; Especially they also can comprise oxidation inhibitor.
Valuably, they do not comprise except that according to the reinforcing filler the present composition.
The part by weight of composition according to the present invention in polymer composition can change in quite wide scope.Generally speaking, it is expressed as the 25-70% of amount of polymers, for example 35-60%.
The present invention also relates to finished product based on above-mentioned polymer composition.As finished product, what can mention is ground mulch, sole, vehicle track parts, tire coverture (particularly tire tread and sidewall), cable car roller bearing, the strip of paper used for sealing that is used for household electrical appliance, sheath, cable and travelling belt.
Following examples explanation the present invention, however be not to limit the scope of the invention.
Embodiment 1
(co-precipitation by sodium aluminate and Tai-Ace S 150 obtains, and contains 70% Al by mixing the 250g pseudobochmite
2O
3Solids content) and 2.7 premium on currency, form Al
2O
3Content is the suspension of 64g/l.By mechanical stirrer (Rayneri Turbo test 200), under 2000 rev/mins speed, stirred this suspension 20 minutes.The pH of suspension is 7.9 then.
Add 309g acetate and lasting stir 20 minute thereafter.Final pH be 2.9 and final volume be 3 liters.Acetate/Al
2O
3Mol ratio is 3.
To put into volume be 5 liters glass autoclave and carry out the hot-pressing processing operation under the following conditions with the suspension that obtains:
-stirring velocity: 560rpm;
-the heating-up time: 1 hour;
-maintenance temperature: 130 ℃;
-the hold-time: 8 hours.
After the operation of this hot-pressing processing, by nozzle atomization device drying, the temperature in of this spraying gun and temperature out equal 400 ℃ and 120 ℃ respectively with the suspension of preparation like this.With aluminum oxide (for the particulate forms) label that obtains is AL1.
Embodiment 2
Preparation is according to composition of the present invention:
A) be this composition of preparation, in water with the aluminum oxide AL1 resuspending of preparation among the embodiment 1 to obtain the Al of 58g/l
2O
3Suspension;
B) in addition, use the embodiment 12 of patent application EP 0 520 862, but do not have the spraying drying step.Therefore, by pressure filter, the precipitated silica dope filtration and the washing that will in the embodiment 1 of patent application EP 0 520 862, obtain, so as the recovery point fire damage lose and to be 79% (with therefore solids content be 21wt%) silica filter cake.(add by machinery and chemical action then corresponding to Al/SiO
2Weight ratio is the sodium aluminate of 3000ppm) with this filter cake fluidization; After this splitting operation, acquisition pH is 6.3 precipitated silica suspension (for pumpable cake form);
C) thereafter, in being equipped with the Rayneri agitator of deflocculate blade, under the speed of 2000rpm, 0.99 liter of aluminum oxide suspension that will obtain in a) stirred 10 minutes; The pH of suspension is 3.2.Abreast, 1 premium on currency is joined at b) in the 713g precipitated silica suspension that obtains, and in being equipped with the Rayneri agitator of deflocculate blade, under the speed of 2000rpm, also stir the suspension 10 minutes of preparation like this;
D) will be at c) in the precipitated silica solution that obtains join c fast) in the aluminum oxide suspension that obtains, carry out mechanical stirring (Rayneri Turbo test 200).Mixture is stirred 15 minutes (2000rpm).The pH of the suspension that obtains is 3.7;
E) will be at d) in the suspension of preparation by nozzle atomization device drying, the temperature in of this spraying gun and temperature out equal 400 ℃ and 120 ℃ respectively.With the composition label that obtains is C1.
Embodiment 3
Prepare two kinds of polymer compositions:
-a kind of comprising according to composition C1 of the present invention (composition 1);
-another kind comprises the direct blends (reference composition R) of the precipitated silica (label is MP1) that obtains after the embodiment 12 of aluminum oxide AL1 and patent application EP 0 520 862.
Table 1
(in the composition of weight part)
| Composition 1 | Composition R | |
| ?SBR (1) | 100 | ?100 |
| ?C1 | 50 | ?0 |
| ?ALl | 0 | ?12.5 |
| ?MP1 | 0 | ?37.5 |
| Silane Si69 (2) | 4 | ?4 |
| Vulkacit D | 1.45 | ?1.45 |
| Stearic acid | 2.5 | ?2.5 |
| Zinc oxide | 2.5 | ?2.5 |
| Oxidation inhibitor (3) | 1.45 | ?1.45 |
| Sulfinyl amine (4) | 2 | ?2 |
| Sulphur | 1 | ?1 |
(1) synthetic styrene-butadiene copolymer (BUNA VSL 5525-1 type) in solution comprises 27.3% oil;
(2) filler/polymkeric substance coupling agent (selling) by Degussa;
(3) N-(1, the 3-dimethylbutyl)-N '-phenyl-p-phenylenediamine;
(4) N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine.
By being 70cm at volume
3Banbury mixer (Brabender type) in, with two steps, elastomerics is carried out hot mechanical treatment and prepares said composition, and average blade speed is 80 rev/mins of temperature up to 110 ℃ of acquisitions, carries out post-processing step after these steps on the external mix machine.
Make the sulfuration of composition be adapted to the sulfuration kinetics of respective mixtures.
Below provide the performance of composition, measure (to the sulfurized composition) according to following standard and/or method:
Rheology and curability
-mooney viscosity: NF T 43005 standards (mooney's viscosimeter is used in the measurement of the Mooney Large (1+4) under 100 ℃);
-sulfuration: NF T 43015 standards.
Use Monsanto 100 S rheometers, especially for minimal torque (C
Min) and torque capacity (C
Max) measurement:
-T
82Corresponding to such time, at this moment between in can monitor mixture-rubber stock at T
82Sulfuration (sulfurized begins) afterwards;
-T
90Corresponding to such time, 90% sulfuration takes place between at this moment.
Mechanical property
-tensile property (modulus, extension at break, tensile strength): NF T 46002 standards.The modulus of x% is corresponding to the stress when tensile elongation is x%.
-tear strength: DIN 53-507 standard.
-Xiao A hardness: ASTM D2240 standard.
After applying power 15 seconds, measure the numerical value of talking about.
Mechanical property (Payne effect)
On mechanical spectrometer (Viscoanalyzer VA2000 is available from Metravib RDS), under various strain rates, measure true modulus (G '), imagination modulus (G ") and tangent loss (tan δ), the loss of this tangent is defined as G " to the ratio of G '.
Test condition is as follows:
Specimen is parallelepiped shape (approximately a, length: 6mm; Width: 4mm; Thickness: 2.5mm).Under the constant frequency of 5Hz, apply the sinusoidal strain that amplitude increases.Under each strain rate, measure G ', G " and tan δ.In following table, Δ G ' is illustrated in to be the modulus G ' that measures down of 0.001 shear strain and to be difference between the modulus G ' that measures under 1 the shear strain, and tan δ
MaxCorresponding to maximum tangent loss as the strained function.
Table 2
| Composition 1 | Composition R | |
| Mooney viscosity | 60 | ?43 |
| Sulfuration: | ||
| C min(in.lb) | 10.9 | ?7.4 |
| T 82(min) | 12 | ?10 |
| T 90(min) | 41 | ?39 |
| C max(in.lb) | 72 | ?69 |
| Mechanical property: | ||
| 100% modulus (MPa) | 2.6 | ?2.6 |
| 300% modulus (MPa) | 11.1 | ?9.9 |
| Extension at break (%) | 490 | ?460 |
| Tensile strength (MPa) | 20.8 | ?17.9 |
| Tear strength (kN/m) | 16.8 | ?10.5 |
| Xiao A hardness | 67 | ?64 |
| Dynamic property (Payne effect) | ||
| ΔG’(MPa) | 11.3 | ?6.8 |
| tanδ max | 0.53 | ?0.49 |
As can be seen, R compares with reference composition, in composition 1 according to the present invention, has better properties compromise.
In addition, relatively demonstration between the photo that in the scanning electronic microscope of two kinds of compositions, obtains, in composition 1 according to the present invention, do not detect agglomerate or aggregate, and under the situation of reference composition R, observe the existence that diameter is about 10 microns agglomeration material; Under the situation of composition 1 according to the present invention, the coarse grain dust dispersion quality of aluminum oxide in polymer composition obtained substantial improvement.
Embodiment 4
Following reactant is incorporated in the static mixer (Lightnin), and concentration and flow are as follows:
-Tai-Ace S 150 (22.75g/1-500l/h)
-sodium aluminate (290g/1-86l/h)
Temperature remains on 60 ℃.
When leaving static mixer, pH be 9 and the aluminium monohydrate concentration that obtains be 60g/l.
Thereafter, this monohydrate is put into the reactor (volume: 12 liters) that comprises the stirring system of being made up of propeller, power of agitator is 500W/m
3
With sodium aluminate (concentration: 290g/l) join in the reactor,, under this temperature, made mixture ageing 3 hours under 90 ℃, pH is remained on 9.
Then, after aging step, aluminum oxide is filtered, washs and drying, as among the embodiment 1.
The aluminum oxide (label is AL2) that obtains has following feature:
-dominant crystallized form: boehmite;
-degree of crystallinity: 85%;
-crystallite dimension: 45 dusts.
Embodiment 5
Preparation is according to composition of the present invention:
A) be this composition of preparation, the aluminum oxide AL2 of preparation among the 491g embodiment 4 is put into water again to obtain 1 liter suspension;
B) in addition, use the embodiment 12 of patent application EP 0 520 862, but do not have the spraying drying step.Therefore, by pressure filter, the precipitated silica dope filtration and the washing that will in the embodiment 1 of patent application EP 0 520 862, obtain, so as the recovery point fire damage lose and to be 79% (with therefore solids content be 21wt%) silica filter cake.(add by machinery and chemical action then corresponding to Al/SiO
2Weight ratio is the sodium aluminate of 3000ppm) with this filter cake fluidization; After this splitting operation, acquisition pH is 6.3 precipitated silica suspension (for pumpable cake form);
C) thereafter, in being equipped with the Rayneri agitator of deflocculate blade, under the speed of 2000rpm, the suspension that will obtain in a) stirred 10 minutes; The pH of suspension is 11.Abreast, 1 premium on currency is joined at b) in the 713g precipitated silica suspension that obtains, and in being equipped with the Rayneri agitator of deflocculate blade, under the speed of 2000rpm, also stir the suspension 10 minutes of preparation like this;
D) will be at c) in the precipitated silica solution that obtains join c fast) in the aluminum oxide suspension that obtains, carry out mechanical stirring (Rayneri Turbo test 200).Mixture is stirred 15 minutes (2000rpm).Dilute this suspension then, so that its final volume is 4 liters.The pH of the suspension that obtains is 8.2;
E) will be at d) in the suspension of preparation by nozzle atomization device drying, the temperature in of this spraying gun and temperature out equal 400 ℃ and 120 ℃ respectively.With the composition label that obtains is C2.
Embodiment 6
As among the embodiment 3, prepare two kinds of polymer compositions:
-a kind of comprising according to composition C2 of the present invention (composition 2);
-another kind comprises the direct blends (reference composition R ') of the precipitated silica (label is MP1) that obtains after the embodiment 12 of aluminum oxide AL2 and patent application EP 0 520 862.
Table 3
(in the composition of weight part)
| Composition 2 | Composition R ' | |
| SBR (1) | 100 | ?100 |
| C2 | 50 | ?0 |
| AL2 | 0 | ?12.5 |
| MP1 | 0 | ?37.5 |
| Silane Si69 (2) | 4 | ?4 |
| Vulkacit D | 1.45 | ?1.45 |
| Stearic acid | 2.5 | ?2.5 |
| Zinc oxide | 2.5 | ?2.5 |
| Oxidation inhibitor (3) | 1.45 | ?1.45 |
| Sulfinyl amine (4) | 2 | ?2 |
| Sulphur | 1 | ?1 |
(1) synthetic styrene-butadiene copolymer (BUNA VSL 5525-1 type) in solution comprises 27.3% oil;
(2) filler/polymkeric substance coupling agent (selling) by Degussa
(3) N-(1, the 3-dimethylbutyl)-N '-phenyl-p-phenylenediamine;
(4) cyclohexyl-2-[4-morpholinodithio base sulfinyl amine.
Below provide the performance of composition, measure (to the sulfurized composition) according to above-mentioned standard and/or method.
Table 4
| Composition 2 | Composition R ' | |
| Mooney viscosity | 40 | ?49 |
| Sulfuration: | ||
| C min(in.lb) | 8.1 | ?8.2 |
| T 82(min) | 5 | ?6 |
| T 90(min) | 40 | ?32 |
| C max(in.lb) | 68 | ?67 |
| Mechanical property: | ||
| 100% modulus (MPa) | 2.8 | ?2.2 |
| 300% modulus (MPa) | 10.8 | ?10.1 |
| Extension at break (%) | 470 | ?450 |
| Tensile strength (MPa) | 19.5 | ?17.7 |
| Tear strength (kN/m) | 10.6 | ?6.6 |
| Xiao A hardness | 65 | ?63 |
| Dynamic property (Payne effect) | ||
| ΔG’(MPa) | 9.1 | ?5.1 |
| tanδ max | 0.56 | ?0.49 |
Equally, as can be seen, R ' compares with reference composition, in composition 2 according to the present invention, has better properties compromise.
In addition, relatively demonstration between the photo that in the scanning electronic microscope of two kinds of compositions, obtains, in composition 2 according to the present invention, do not detect agglomerate or aggregate, and under the situation of reference composition R ', observe the existence that diameter is about 10 microns agglomeration material; Under the situation of composition 2 according to the present invention, the coarse grain dust dispersion quality of aluminum oxide in polymer composition obtained substantial improvement.
Claims (20)
1. composition that obtains by dry suspension, this suspension comprises, on the one hand, form factor less than 15 aluminium oxide particles A and, on the other hand, can be in polymeric media dispersive precipitated silica particle B.
2. according to the composition of claim 1, it is characterized in that by mixing the suspension of at least a form factor less than 15 aluminium oxide particles A, with at least a can be in polymeric media the suspension of dispersive precipitated silica particle B, and obtain described suspension.
3. according to the composition of one of claim 1 and 2, it is characterized in that form factor can not disperse less than 15 aluminium oxide particles A in polymeric media.
4. according to the composition of one of claim 1-3, it is characterized in that carrying out described drying by spraying drying.
5. according to the composition of claim 4, the temperature out that it is characterized in that the spraying gun that during drying adopts is less than 170 ℃.
6. according to the composition of one of claim 4 and 5, it is characterized in that carrying out drying by the nozzle atomization device.
7. according to the composition of one of claim 1-6, it is characterized in that pore distribution that described precipitated silica particle B has makes that by diameter be the pore volume that the hole of 175-275 dust forms, be at least by diameter and be less than or equal to 50% of pore volume that the hole of 400 dusts forms.
8. according to the composition of one of claim 1-6, it is characterized in that described precipitated silica particle B has the ultrasonic wave deagglomeration factor F greater than 5.5ml
DWith after the ultrasonic wave deagglomeration less than the middle footpath of 5 μ m
50
9. composition according to Claim 8 is characterized in that pore distribution that described precipitated silica particle B has makes that by diameter be the pore volume that the hole of 175-275 dust forms, and is at least by diameter to be less than or equal to 50% of pore volume that the hole of 400 dusts forms.
10. according to the composition of one of claim 1-9, it is characterized in that described precipitated silica particle B has the ultrasonic wave deagglomeration factor F greater than 11ml
DWith after the ultrasonic wave deagglomeration less than the middle footpath of 2.5 μ m
50
11. according to the composition of one of claim 1-10, the CTAB specific surface area that it is characterized in that described precipitated silica particle B is 50-240m
2/ g.
12., it is characterized in that the suspension that aluminum oxide passes through hot-pressing processing boehmite or pseudobochmite obtains according to the composition of one of claim 1-11.
13., it is characterized in that hot-pressing processing carried out 6-10 hour under 110-150 ℃ maintenance temperature according to the composition of claim 12.
14., it is characterized in that aluminum oxide is the crystallization monohydrate according to the composition of one of claim 1-11, be mainly the form of boehmite, it is by obtaining sodium aluminate and Tai-Ace S 150 co-precipitation.
15. according to the composition of one of claim 1-14 purposes as the reinforcing filler in the polymer composition.
16., it is characterized in that described polymer composition is based on second-order transition temperature and is-150 ℃ to+300 ℃ at least a polymkeric substance or multipolymer according to the purposes of claim 15.
17. the polymer composition based at least a polymkeric substance or multipolymer, it comprises reinforcing filler, it is characterized in that described reinforcing filler is by forming according to the composition of one of claim 1-14.
18., it is characterized in that the second-order transition temperature of described polymkeric substance or multipolymer is-150 ℃ to+300 ℃ according to the polymer composition of claim 17.
19., it is characterized in that it comprises at least a coupling agent and/or at least a restorative in addition according to the polymer composition of one of claim 17 and 18.
20. finished product based at least a composition among one of claim 17-19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR99/10636 | 1999-08-13 | ||
| FR9910636A FR2797451B1 (en) | 1999-08-13 | 1999-08-13 | COMPOSITION FOR USE AS A REINFORCING FILLER IN POLYMER COMPOSITIONS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1372583A CN1372583A (en) | 2002-10-02 |
| CN1189522C true CN1189522C (en) | 2005-02-16 |
Family
ID=9549244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00812361.6A Expired - Fee Related CN1189522C (en) | 1999-08-13 | 2000-08-11 | Composition for used as reinforcing filler in polymer composition |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1203056B1 (en) |
| JP (1) | JP3628652B2 (en) |
| KR (1) | KR20020043555A (en) |
| CN (1) | CN1189522C (en) |
| AT (1) | ATE374801T1 (en) |
| AU (1) | AU7011900A (en) |
| BR (1) | BR0013266A (en) |
| CA (1) | CA2381705C (en) |
| DE (1) | DE60036622T2 (en) |
| FR (1) | FR2797451B1 (en) |
| MX (1) | MXPA02001438A (en) |
| WO (1) | WO2001012729A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002332381A (en) * | 2001-05-10 | 2002-11-22 | Sumitomo Chem Co Ltd | Rubber composition and tire using the same |
| EP1580223A1 (en) * | 2004-02-25 | 2005-09-28 | SASOL Germany GmbH | Polymers including boehmite fillers |
| FR2872817B1 (en) * | 2004-07-07 | 2006-09-22 | Michelin Soc Tech | RUBBER COMPOSITION FOR TIRE BASED ON A REINFORCING METAL HYDROXIDE |
| EP1957684B1 (en) * | 2005-09-16 | 2010-12-08 | H.C. Starck GmbH | Reduction method |
| KR100967053B1 (en) * | 2007-12-27 | 2010-06-29 | 주식회사 포스코 | Laser processing apparatus |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3243404A (en) * | 1962-04-02 | 1966-03-29 | Gen Electric | Silyl amine processing aids for polysiloxane elastomers |
| FR2453880A1 (en) * | 1979-04-13 | 1980-11-07 | Rhone Poulenc Ind | NOVEL SILICA-BASED PIGMENT IN BALL FORM, PROCESS FOR OBTAINING THE SAME AND APPLICATION, IN PARTICULAR AS REINFORCING FILLER IN ELASTOMERS |
| US5674932A (en) * | 1995-03-14 | 1997-10-07 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
| FR2761692B1 (en) * | 1997-04-04 | 2000-08-11 | Talc De Luzenac | PROCESS FOR OBTAINING HIGH LAMELLARITY MINERAL POWDER AND APPLICATIONS IN PARTICULAR FOR THE REINFORCEMENT OF PLASTIC MATERIALS |
-
1999
- 1999-08-13 FR FR9910636A patent/FR2797451B1/en not_active Expired - Fee Related
-
2000
- 2000-08-11 AU AU70119/00A patent/AU7011900A/en not_active Abandoned
- 2000-08-11 KR KR1020027001871A patent/KR20020043555A/en not_active Application Discontinuation
- 2000-08-11 MX MXPA02001438A patent/MXPA02001438A/en unknown
- 2000-08-11 JP JP2001517619A patent/JP3628652B2/en not_active Expired - Fee Related
- 2000-08-11 AT AT00958673T patent/ATE374801T1/en not_active IP Right Cessation
- 2000-08-11 CA CA002381705A patent/CA2381705C/en not_active Expired - Fee Related
- 2000-08-11 DE DE60036622T patent/DE60036622T2/en not_active Expired - Lifetime
- 2000-08-11 EP EP00958673A patent/EP1203056B1/en not_active Revoked
- 2000-08-11 WO PCT/FR2000/002307 patent/WO2001012729A1/en active IP Right Grant
- 2000-08-11 BR BR0013266-7A patent/BR0013266A/en not_active IP Right Cessation
- 2000-08-11 CN CN00812361.6A patent/CN1189522C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP1203056A1 (en) | 2002-05-08 |
| KR20020043555A (en) | 2002-06-10 |
| BR0013266A (en) | 2002-07-09 |
| CA2381705A1 (en) | 2001-02-22 |
| JP3628652B2 (en) | 2005-03-16 |
| WO2001012729A1 (en) | 2001-02-22 |
| CA2381705C (en) | 2005-10-25 |
| FR2797451A1 (en) | 2001-02-16 |
| ATE374801T1 (en) | 2007-10-15 |
| CN1372583A (en) | 2002-10-02 |
| DE60036622T2 (en) | 2008-07-03 |
| AU7011900A (en) | 2001-03-13 |
| FR2797451B1 (en) | 2001-10-12 |
| MXPA02001438A (en) | 2002-07-02 |
| DE60036622D1 (en) | 2007-11-15 |
| EP1203056B1 (en) | 2007-10-03 |
| JP2003507518A (en) | 2003-02-25 |
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